Manufacture of 1, 3, 5-ethylxylene



my l954 D. A. MCCAULAY ETAL MANUFACTURE oF 1,3,5-ETHYLXYLENE Filed March 22, 1952 m @t i Patented July 13, 1954 UNITED! STATES MANUFACTURE F 1,3,5-ETHYLXYLENE David` A. McCaulay, Chicago, Ill., and Arthur P. Lien, Highland, Ind., assignors to Standard Oil Company, Chicago, Ill., a corporation of Indiana Application March 22, 1952, Serial No. 277,966

Claims.

This invention relates to the manufacture of ethylxylenes by the reaction of xylene and ethylbenzene. More particularly, the invention relates to the preparation of symmetrical 1,3,5-ethylxylene. Still more particularly, the invention relates to the preparation of a high purity 1,3,5- ethylxylene.

The commercial polystyrene resins have the disability of a softening point lower than the boiling point of water. It is known that resins prepared from dimethylstyrene have a softening point higher than the boiling point of water. Ethylxylenes with an ortho arrangement of a methyl and the ethyl group dehydrogenate to methylindenes, which are very dicult to separate from the dimethylstyrene. The methylindenes act as plasticizers and lower the softening point of the polydimethylstyrene, the presence of about 6% of these contaminants in the resin lowers the softening point below the boiling point of water. In the prior art processes, the ethylxylenes having the undesirable ortho relation between a methyl and the alkyl group are the predominant product.

It is an object of this invention to prepare ethylxylene by the reaction of xylene and ethylbenzene under controlled conditions. Another object is the preparation of 1,3,5-ethylxylene of high purity. Still another object is the manufacture of 1,3,5-ethylxylene in high purity and in good yield by the reaction of xylene and ethylbenzene under controlled conditions and in the presence of a treating agent consisting of liquid HF and TiFi.

We have previously discovered that polyalkylbenzenes, such as, xylene, diethylbenzene, ethylxylene react with liquid HF and titanium tetrafluoride to form a complex containing 2 mols of TiF4 and probably 1 mol of HF for each mol of polyalkylbenzene. It is believed that HF is present in the complex because no complex is formed between TiFi and xylene in the absence of liquid HF. Under the conditions of this process benzene, toluene and ethylbenzene do not form a complex with TiF4 and liquid HF. The complex is extremely soluble in liquid HF and sufcient liquid HF must be present in the reaction zone to form the complex and also to dissolve the complex itself.

The liquid HF used in the process should be substantially anhydrous, i. e., the liquid HF should not contain more than about 1 to 2% of water. The amount of liquid HF needed in the process is between at least about 2 mols and about 50 mols per mol of xylene present in the feed. Put in another way, the amount of liquid HF used should be between about and 1,000 volume percent, based on xylene. Preferably, the liquid HF should be between about 100 and 500 volume percent.

TiF4 is a crystalline solid having a boiling point of 543 F. 'Ihe solid is only slightly soluble in liquid HF. The solubility of TiF4 in liquid HF is enormously increased when a polyalkyl aromatic hydrocarbon is brought into contact with the 'I'iF4 in the presence of liquid I-Hi. Thus a slurry of TiF4 and liquid HF is quickly converted to a clear, reddish liquid when the slurry is contacted with a sufficient amount of xylene.

Benzene and ethylbenzene are soluble in liquid HF to the extent of 3 or 4 Volume percent at ambient temperatures. The presence of a TiF-i- HF-xylene complex in the liquid HF markedly increases the solubility of benzene and ethylbenzene in the liquid HF. Apparently the complex acts as a solubility promoter for non-complexible aromatic hydrocarbons. The ability of liquid HF to dissolve benzene and ethylbenzene increases with increase in the amount of complex present in the liquid HF. The ability of liquid HF to take up ethylbenzene is very markedly increased by the conversion of ethylbenzene to diethylbenzene. Liquid HIE1 and TiF4 rapidly disproportionate ethylbenzene to diethylbenzene; the diethylbenzene complexes with TiF4 and HF and passes into solution in the form of a complex.

In addition to the formation of diethylbenzene, the disproportionation of ethylbenzene results in the formation of some triethylbenzene. It has been found that the presence of a TiF4-HF-xylene complex in the liquid HF tends to suppress the formation of triethylbenzene. Nearly complete disproportionation of the ethylbenzene to diethylbenzene can be obtained by using enough TiF4E to complex all the xylene present and all the diethylbenzene formed in the reaction. It has been discovered that the diethylbenzene-complex and the xylene-complex will slowly react to form ethylxylenes (which are complexed) ethylbenzene and benzene. Furthermore, it has been discovered that the ethylxylene reaction product is predominantly a symmetrical 1,3,5-ethylxylene; and by controlling the conditions of the reaction, it is possible to limit the ethylxylene produced to the desired 1,3,5-ethylxylene isomer exclusively.

The amount of TiF4 needed in the process is at least that amount which will bring into the liquid HF phase all of the xylene and ethylbenzene charged to the reaction zone. When the mol ratio of xylene to ethylbenzene in the feed is at least 1, the minimum amount of TiF4 should be about 1.4 mols per mol of xylene in the feed. More than the minimum amount of TiF4 may be used; however, it is preferred to limit the amount of TiF4 present to that amount which will be in the liquid HF phase either in the form of a complex or in physical solution. The presence of undissolved TiF4 in the reaction zone results in the formation of undesired side reaction products.

Although the process works satisfactorily for the production of ethylxylenes when more than the amount of TiF4 needed to complex all the xylenes charged is present in the reaction zone, it is preferred to use less than this amount, i. e., less than 2 mols of TiF4 per mol of xylene v charged. When using at least 2 mols of TiF4 per mol of xylenefthe time for attaining a reaction product in which ethylxylene is the predominant product is increased somewhat over the process using less than 2 mols of TiF4,. Hereinafter, mols of TiF4 is intended to mean mois of .'IiFi per mol of xylene charged to the reaction zone. preferred to limit the amount of 'I'iF4 in the reaction zone to the amount whichwill solubilize al1 the xylene and ethylbenzene into the liquid HF phase. In general, it is preferred to use between about 1.4 and 1.9 mols of -TiF4. presence of dissolved non-complexed xylene not only speeds up the ethylxylene reaction, but alsov appears to reduce the amount of diethylbenzene present in the reaction products. By the use of a system consisting essentially of xylene-complex, free-xylene, ethylbenzene and liquid HF, it is possible to produce a reaction product wherein the C10 aromatic hydrocarbon product contains in excess of 95% of 1,3,5-ethylxylene, i. e., high purity material.

In general, the xylene to ethylbenzene molal ratio must be at least 1 in order to obtain appreciable yields of ethylxylene. Higher ratios aid in reducing the amount of diethylbenzene present in the reaction-product. In general, the preferred minimum .xylene/ethylbenzene ratio is about 1.5; the xylene/ethylbenzene ratio may be as great as 10 or more. It is preferred to operate at a xylene/ethylbenzene ratio between about 2.5 and 5.

Although the mechanism of this process is not fully understood, it is believed that the ethyl group adds to the xylene and several, if not all, of the isometric ethylxylenes are formed. After the ethyl groupv addition, isomerization takes place. Hereby the ethylxylene isomers are converted to the symmetrical 1,3,5-ethylxylene configuration. Apparently this configuration forms the most stable complex with HF and TiF4.

It has been found that the distribution of ethylxylene isomers in the reaction product is dependent upon both temperature and reaction time. The kreaction temperature that may be used is limited by the fact that at higher temperatures the unreacted xylenes disproportionate to form polymethylbenzenes, toluene and benzene. The tendency of the ethylxylenes to crack and form tarry materials imposes an upper limitof about 160`F on the reaction temperature. It has been found that xylenes disproportionate in appreciable amounts when held at temperatures in excess of 100 F. for severallhours; for example, when a single phase homogeneous system of meta-xylene, TiF4 and HF was held at 86 F. forv 24'hours, about 2% of the meta-xylene was disproportionated into toluene and trimethylbenzene. In order to avoid the loss of Xylene and ethylxylenes, the reaction temperature should be maintained at the lowest point consistent with satisfactory reaction-times and with conversion to the desired 1,3,5-ethylxylene form. Lowering the temperature of the reaction decreases the rate of reaction and of the isomerization of the ethylxylenes. However, temperatures as low as F. or lower can be used if the correspondingly longer reaction time is used. In the operable temperature range, the amount of ethylbenzene reacted reaches a maximum of about 90%. At

It iS 160 F., the maximum conversion is reached in about 30 minutes and 2 hours; the longer times correspond to the lower temperatures.

The xylenes charged to this process can be any one of the three isomers or any mixture thereof. The most desirable xylene is the meta-isomer. lVIeta-xylene reacts with ethylbenzene to form 1,3,5-ethylxylene to the virtual exclusion of the other ethylxylener isomers. When using paraxylene,y ortho-xylene, mixtures thereof, or mixtures of these andmeta-xylene, it may be necessary to extend the reaction time beyond that needed toi complete the xylene-ethylbenzene reaction, in order to isomerize the ethylxylene mixtureand; obtain 1,3,5-ethylxylene of high purity. Para-xylene and ortho-xylene disproportionate much more readily than meta-xylene. In general, lower vtemperatures should be used when either or both of these isomers are present in the charge to the reaction. About 140-a F. is the upper temperature limit and a suitable operating temperature is about 120 F.

The following runs illustrate the experimental procedure used and the results obtainable by this process. The runs were carried out in a 1570 ml. carbon steel autoclave fitted with a 1725 R. P. M. stirrer. The desired amounts of TF4, xylene, ethylbenzene andV liquid HF were added to the reactor. The temperature of the reactor contents was maintained at a selected temperature for a selected reaction time. The contents of the reactor were withdrawn into a Dry-Ice cooled flask containing crushed ice. In each run insofar as could be determined by visual observation, only a liquid HF phase and some undissolved TiFr was present in the reactor.

The flask containing the reaction products was allowed to warm to room temperature. The supernatant hydrocarbons-displaced from their TiF4-HF complexes by the water-were separated from the aqueous acid phase. The hydrocarbons were washed with dilute aqueous caustic to remove traces of HF. The reaction products were fractionated to a number ofv close boiling cuts by means of a 30 theoretical plate column. Each cut was analyzed by ultraviolet absorption or infrared absorption, together with refractive index and specific gravity measurements. The properties of the high purity ethylxylene product were compared with those given by Birch et al. in Petroleum Preprints, A. C. S. Spring 1948, p. 135. The data for runs 1, 2 and 3 are presented below.

m1. mols ml. Inols m1. mols Reactor Charge:

m-xylene 100 0. 8 100 0. 8 100 0. 8 Etllylbenzene..L 100 0.8 100 0.8 100 O. 8 HF 500 25 500 25 500 25 TiF4 388 g 3. 2 388 g 3. 2 388 g 3. 2

Hydrocarbon Recovery, wt. percent. 90 S2 85 Production Distribution, mol percent:

Benzene 20. 7 31. 2 32. 6 m-Xylene 49. 6 26. 0 12. 3 Ethylbcnzene. 10.1 3. 2 3. 4 1,3-diethylbenzene. 14. 5 7. l 4. 8 l,3,5-ethy1Xy1ene 1.3 26.0 40. 8 C12 aromatics 3.8 6. 5 0.1 Ethylbenzenc conversion, percent 93 93 Xylcne to ethylxylene,

percent 2 50 75 The accompanying drawing shows one embodiment of this process for the production of high purity 1,3,5-ethylxylene by the reaction of xylenes and ethylbenaene. It is to be understood that this embodiment is shown for purposes of illustration only and that many other variations can be readily devised by those skilled in the art. It is to be further understood that pumps, numerous valves and other pieces of process equipment have been omitted because these can be readily supplied to the embodiment by those skilled in the art.

In this illustration the charge consists of a mixture of m-xylene, p-xylene and ethylbenzene. The charge was derived from the product of the hydroforming of a virgin naphtha. The xylene cut which contained about 21% o-xylene was fractionated in order to sepa-rate the o-xylene. The remainder consists of: ethylbenzene, m-xylene, 61 and p-xylene, 24%.

The charge from source Il is passed through line l2 into line E3. In the case where the feed contains a high percentage of ethylbenzene, xylenes can be added from source l5 by way of valved line l1 into line I3 to increase the xylene to ethylbenzene ratio.

Liquid HF from source I3 is passed by way of line 2! into vessel 22, which vessel 22 is provided with agitating means not shown. Finely divided IiF4 from source 23 is passed by way of line 24 into vessel 22. Many methods are known for introducing a finely divided solid into a line and for conveying the material into a closed vessel, e. g., storage 23 may be equipped with a star valve at the exit thereof and line 24 may be equipped with conveying flights for moving the solid. In vessel 22 the liquid HF and the TiF4 form a slurry, as in this case more 'IiF4 is used than is soluble in the liquid HF. This slurry is passed from vessel 22 into line 25 where it meets the feed from line i3.

Another method of introducing TiF4 into the system is to add TiCh-a liquid-into vessel 22 where the chloride reacts with HF to produce TiF4. Additional liquid HF must be added to vessel 22 to participate in the reaction and to leave the desired amount of liquid HF for use in the reaction zone. When adding TiCh, means for venting HCl should be provided on vessel 22.

In this illustration we use 300 volume percent of liquid HF based on xylene in the feed and 1.8 mols of l'iFx per mol of xylene present in the feed. The contents of line 25 are passed into mixer 21, which mixer is provided with a heat exchange coil 23. The reaction of the HF, TiF4 and xylene to form the complex is exothermic and the heat exchange coil 28 is provided to enable the temperature of the reaction mixture to be controlled. In mixerZ'! the liquid HF, TiF4 and feed are agitated and form a single homogeneous liquid phase consisting essentially of liquid HF, complexed-xylene, free-xylene and ethylbenzene.

The reaction mixture is passed from mixer 21 by way of line 23 into reactor 3l. Reactor 3l is provided with a heat exchange coil 32. In this example the reaction is carried out at a temperature of about 130 F. The reaction mixture is held in reactor 3l for a time suiiicient to obtain the desired degree of conversion of the ethylbenzene and to substantially complete the isomerization of ethylxylenes to the desired 1,3,5-ethylxylene isomer. At the operating conditions used in this illustration a suitable reaction time is about 60 minutes.

The contents of reactor 3| are passed through line 33, heat exchanger 34 and line 36 into stripper 31 which is provided with internal heater 38. The contents of reactor 3| may be cooled quickly in exchanger 34 in order to decrease the degree of disproportionation of the xylene which takes place readily at this elevated temperature. In stripper 31 the complex is decomposed by removing the HF. In order to avoid the formation of undesirable by-products through disproportionation and cracking, the removal of the HF is carried out under vacuum. The HF removal operation is facilitated by the use of a stripping agent. Here butane from source 4l is passed by way of line 42 into stripper 31 near the bottom thereof. The stripping agent should be substantially inert to the catalytic action of HF.

The HF and butane vapors pass out of stripper 31 through line 4B, vacuum pump 41, line 48 into cooler 49. In cooler 45 the HF and butane are condensed and the liquid is passed by way of line 5| into settler 52. The upper layer of butane is separated from the lower layer of HF in settler 52 and is recycled to line 42 by way of line 53 and other lines not shown. The lower HF layer is withdrawn from settler 52 by way of valved line 54.

In the bottom of stripper 31 there appears upon the removal of the HF a slurry of extremely nely divided TiF4 in the hydrocarbon reaction products. The particle size of the TiF4 varies somewhat with the operation of stripper 31 and may in some cases be almost colloidal in nature. The slurry of TiF4 and hydrocarbons is withdrawn from stripper 31 by way of valved line 56 and is passed into lter 51. Filter 51 may be any type of HF-resistant and HF-vapor tight filter which is adapted to the removal of extremely nely divided solids. Instead of a filter a centrifugal separator may be used. The TiFi is retained in filter 51 and the hydrocarbons are passed into valved line 59. It is to be understood that even though only one lter is shown, for continuous operation two or more filters would be used.

The TiF4 is removed from filter 51 by means of a backwashing operation with liquid HF from line 54. The slurry of liquid HF and TiF4 is passed from filter 51 by way of valved line 6I to vessel 22 for reuse in the process.

The hydrocarbons pass out of iilter 51 through line 59 through heater 53 and line G4 into fractionator 66, which is provided with reboiler 51. The unreacted xylene and ethylbenzene pass overhead through line 1l and are condensed in cooler 12. This fraction may be sent to storage by way of line 13 or may be recycled to line I3 by way of valved line 14. In this illustration only a very small percentage of C12 aromatic hydrocarbons is formed in the reaction. In addition to the C12 aromatics, a very slight amount of diethylbenzene is also formed. The diethylbenzene and C12 aromatic hydrocarbons form less than about 5% of the total reaction products. Thus a high purity 1,3,5-ethylxylene fraction is withdrawn from the bottom of fractionator 54 through line 15 and is sent to storage not shown. If desired, the slight amount of C12 aromatic hydrocarbons may be removed by distillation from the reaction product in order to obtain a still higher purity ethylxylene product.

Although a iilter technique has been shown for the separation of TiF4 from the reaction product other methods may be utilized, e. g., the slurry of TiF4 and reaction products may be passed from stripper 31 through a heat exchanger and passed into a ash chamber where the hydrocarbons are taken overhead, leaving TiF4 behind. The TiF4 may then be removed from the flash chamber by slurrying with This ashing technique may be made continuous by using two iiash chambers operating alternately. Other methods of making this separation can be readily devised by those skilled in the art.

This application is a continuation-in-part of our copending application Serial No. 272,654, led February 20, 1952, and entitled Xylene Separation With Liquid HF and TiFi.

Having described the invention, claimed is:

1. A method for the preparation of high purity 1,3,5-ethy1xylene by the reaction of Xylene and ethylbenzene, which method comprises the steps of contacting xylene and ethylbenzene in an amount between about 1.5 and 10 mols of xylene per mol of ethylbenzene, with liquid HF in an amount between about 20 and 1,000 volume percent per volume of said Xylene, and with between about 1.4 and 1.9 mols of TiF4 per mol of said xylene, maintaining said materials at a temperwhat is aturebetween about 45 and 160 F'. for a time between about 15 minutes and 50 hours, in such manner that the longer time corresponds to the lower temperature, removing HF and TiF4 from the hydrocarbons and separating high purity 1,3,5-ethylxylene from said hydrocarbons.

2. The process of claim 1 wherein the mol ratio of Xylene to ethylbenzene is between about 2.5 and 5.

3. The process of claim 1 wherein the amount of liquid HF is between about 100 and 500 volume percent, based on Xylene.

4. The method of claim 1 wherein said Xylene is meta-xylene.

5. The method of claim 1 wherein said xylene is a mixture of at least two isomeric Xylenes.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,385,524 Mattox Sept. 25, 1945 2,514,866 Hovey July 11, 1950 2,564.073 Lien et al Aug.. 14. 1951 

1. A METHOD FOR THE PREPARATION OF HIGH PURITY 1,3,5-ETHYLXYLENE BY THE REACTION OF XYLENE AND ETHYLBENZENE, WHICH METHOD COMPRISES THE STEPS OF CONTACTING XYLENE AND ETHYLEBENZENE IN AN AMOUNT BETWEEN ABOUT 1.5 AND 10 MOLS OF XYLENE PER MOL OF ETHYLBENZENE, WITH LIQUID HF IN AN AMOUNT BETWEEN ABOUT 20 AND 1,000 VOLUME PERCENT PER VOLUME OF SAID XYLENE, AND WITH BETWEEN ABOUT 1.4 AND 1.9 MOLS OF TIF4 PER MOL OF SAID XYLENE, MAINTAINING SAID MATERIALS AT A TEMPERATURE BETWEEN ABOUT 45* AND 160* F. FOR A TIME BETWEEN ABOUT 15 MINUTES AND 50 HOURS, IN SUCH MANNER THAT THE LONGER TIME CORRESPONDS TO THE LOWER TEMPERATURE, REMOVING HF AND TIF4 FROM THE HYDROCARBONS AND SEPARATING HIGH PURITY 1,3,5-ETHYLXYLENE FROM SAID HYDROCARBONS. 